Purification of aliphatic hydrocarbons



April 29, 1952 2 SHEETS-SHEET l Filed Jan. 5, 1949 F/GJ.`

0%/1 ma El OZA 00715 @fw-M April 29, 1952 A. E. HIRSCHLER PURIFICATION OF ALIPI-IATIC HYDROCARBONS MMA;

Patented Apr. 29, 1952 UNITED STATES PATENT OFFICE PURIFICATION or ALIPHATIC HYDRoCAnBoNs ration of New Jersey Application January 5, 1949, Serial. No. 6 .9,343

12 Claims. l

This invention relates to the separation of hydrocarbons of the aliphatic or parafnic type. The` invention is particularly directed to a method of preparing a paraflin hydrocarbon of high purity from a mixture containing one or more other paraiiin hydrocarbons of the same molecular weight as that of the desired hydrocarbon.

In the preparation of individual hydrocarbons by organic synthesis, it is seldom that the desired hydrocarbon may be produced directly in a high state of purity. Generally a mixture of hydrocarbons is formed, which includes isomers of the desired hydrocarbon and other related compounds Which may boil relatively close to the desired' hydrocarbon. A usual procedure of purification involves distillation under fractionating conditions whereby removal of compounds having boiling points suiciently diierent from that of the desired hydrocarbon may be accomplished. It is often the case, however, that a high degree of purity may not be attained in this manner, or may be obtained only with great difficulty, due to the proximity of boiling points of the various compounds. Likewise, in the separation of a particular hydrocarbon from a complex hydrocarbon mixture such as petroleum or coal tar fractions, it is often extremely difficult to segreate the desired component as a product of high purity due to the presence of other compounds of close boiling points. While the use along with straight distillation of other procedures, such as solvent extraction and azeotropic 1 distillation, has resulted in improved separations in certain cases, generally speaking it has not been practical heretofore to produce hydrocarbons of high purity from mixtures containing very closely related hydrocarbons. Usually the best that has been done; from a practical aspect is to prepare hydrocarbons of technical purity, such as in concentrations in the order of 80% to 95%. To produce hydrocarbons in a high state of purity, for example in concentrations better than 95%', from mixtures containing close boiling compounds of similar hydrocarbon type heretofore has been extremely difticult and, in many cases, practically impossible.-

The present invention provides an improved method whereby relatively pure hydrocarbons of the aliphatic class may be prepared. It is especially useful when the starting material contains as the impurity a minor amount of one or more related hydrocarbons boiling close to the desired compound, as when its isomers con"titute the impurity. The purication is accomplishedl 2 according to the inventionvby selective adsorption utilizing silica gel as the adsorbent.

It is well known that hydrocarbons may be separated to an extent according to chemical type by selective adsorption on silica gel or like adsorbents. This procedure has been utilized to separate aromatics and olefins from saturated hydrccarbons (i. e. naphthenes and parailins). It is also known that two compounds of a given hydrocarbon class which have greatly different molecular Weights may exhibit sufficient differences in adsorbability so that partial separation may be effected by selective adsorption. However, it has heretofore been thought that hydrocarbonsof the same class which do not diier greatly in molecular Weight, and particularly hydrocarbons having the same molecular Weight have adsorbabilities so nearly the same that for all practical purposes no separation could be effected by adsorption.

I have found that all paranic hydrocarbons having the fame number of carbon atoms per molcoule nevertheless have suiiiciently different adsorbabilities to be separable by selective adsorpton on silica gel. The present invention thus provides a process for separating any two liquid paraiiinic hydrocarbons of the same molecular weight. Briey, the process comprises subjecting the mixture of such hydrocarbons to treatment in liquid phase with silica gel to selectively adsorb one of them from the charge and separating from the silica gel one or more fractions in' which the proportion of the other hydrocarbon to the selectively adsorbable hydrocarbon is higher than in the starting mixture or, in other words, which contains the other parafn in more nearly pure state. When the paraiiin which is selectively adsorbed is the hydrocarbon that is desred in pure form, it may be obtained by disvpacing the adsorbate from the silica gel by means of a suitable desorbing agent.

I have further found that mixtures of parafiins exhibit'adsorption behaviors which may be classiiied in two general types. One type occurs where one of the paraffin components is selectively adsorbed from the mixture throughout a portion cf the concentration range, while the other parain is the component which is selectively adsorbed throughout the remainder of the concentration range. Many pairs of parafinic hydrocarbons behave in this manner. The other type occurs where one of the parailins is the selectively adsorbable component throughout the whole concentration range. Numerous other paraffin mixtures exhibit this type of behavior.

All isomeric parafns conform to one or the other type of behavior. It is not always possible to predict inadvance which type of behavior will be exhibited by any given pair of hydrocarbons; so that in any such case if it is desired to know with certainty in advance just which type of behavior will be encountered it is necessary to predetermine the eiect of proportions of the components on the relative adsorabilities. This is not necessary in order to insure operability of the process, however, since a separation Will always be eiected in accordance with the invention re- 'rium with a given amount of adsorbent and the amount of component adsorbed. (The latter value is the apparent amount as customarily calculated from the change in composition of the mixture before and after adsorption assuming no adsorption of the other component.)

Figure 1 is representative of the type of adsorption isotherm obtained where one of the components is selectively adsorbed over part of the concentration range and the other component is selectively adsorbed over the remainder of the range. Figure 2 illustrates the adsorption isotherm where one oi. the components is selectively adsorbable throughout the whole concentration range. Figure 3-represents the same type of behavior as shown in Figure 1, except that one of the components is selectively adsorbed over a much wider portion of the concentration range than is the other component. Most paraffin hydrocarbons form with silica gel a system of the type illustrated by Figures l and 3, or in other words, exhibit a so-called S-type adsorption isotherm, as distinguished from a U-type isotherm such as shown in Figure 2.

With the type of behavior as shown in Figure 1, component A is selectively adsorbable from any mixture of the hydrocarbons, A and B, which has a composition lying between A and that represented by point M which is the composition corresponding to the point where the adsorption isotherm crosses the horizontal line. On the other hand, component B is selectively adsorbable from any mixture where the proportion of A is above that represented by point M. Either component may therefore be prepared in a highly purified state, depending upon which side of point M the starting mixture composition falls. For

"example, by starting with a technical grade of fthe A component, say a mixture which contains mixtures of parafn hydrocarbon pairs' comes more difcult as the amount of the impurity decreases. An example of a hydrocarbon mixture which exhibits the type of behavior shown in Figure 1 is n-octane and 2,2,4-trimethylpentane.

Where the behavior is of the type shown in Figure 2 the A component is selectively adsorbed from the mixture regardless of its concentration. When a mixture of this type is treated with silica gel, the A component will always be selectively removed, thus yielding the B component in a more nearly pure form. Also, by desorbing the A component from the used adsorbent in a suitable manner, A likewise may be obtained in purified form. An example of a mixture forming this type of system is 2,2,4-trimethylpentane and 2,3,3- trimethylpentane.

Figure 3 illustrates a system of the same type as illustrated in Figure 1 but wherein the A cornponent is selectively adsorbable over a great part of the concentration range, for example, when its concentration lies between 0% and 90%. A mixture of this type is formed by 2,4-dimethylpentane and 2,3-dimethylpentane with the 2,4- compound corresponding to the A component. With mixtures of this type, the B component is not as readily removable when it is present in small amount as is A when it is present in low concentration. Nevertheless, B may be selectively removed when the starting mixture contains A in any proportion above that represented by point M', and the lower the concentration of B the more e'fective is its removal. If the concentration of B in the starting mixture is low to begin With (say 2 or 3% or the like), further effective purification of A may readily be accomplished. As previously stated, this is in contrast to other methods where further purication becomes extremely diicult when a low concentration of one of the components is reached.

It should be noted that with hydrocarbons which form the S-type adsorption isotherm (Figures l and 3), there is a theoretical point (M or M) at which the hydrocarbons will have the same adsorbability and therefore would not, theoretically, be separable by selective adsorption. In actual practice, however, there is no condition at which separation is absolutely incapable of being effected. There are several reasons why at least some separation will occur even with a starting mixture which approximates, as closely as possible, the composition corresponding to the aforesaid theoretical point. One is that a mixture corresponding absolutely to such point could never be encountered, due to the fact that it is a point, as distinguished from a zone, and therefore is dimensionless and can only be approximated but never exactly reached. Thus, some separation will always result, although the degree of separation might not be commercially practicable where the starting mixture composition approaches too closely to that corresponding to the theoretical point. Another reason depends upon the fact that, as I have discovered, this theoretical point changes to a substantial extent as the temperature of operation changes. In actual practice, it would never be the case that exactly the same temperature would obtain throughout the whole mass of silica gel being used to treat the starting mixture. There would always be some diierences in temperature throughout the adsorbent so that some separation would necessarily result regardless of the starting mixture composition. Still another reason why a separation would always be eiected to some extent is due to the fact, as I have further discovered, that the individual particles of ad.- sorbent within any given batch of silica gel vary somewhat in adsorptive qualities. For example, it has been found that the theoretical point will be different depending upon the size of the `particles segregated from a given batch of theadsQrbent. Even if it were possible that the starting .mixture corresponded exactly to the theoretical point for some of the particles, it would not so correspond for other particles constituting the adsorbent mass.

It is therefore apparent that regardless of what the particular proportion of parains in the starting mixture may be, a separation, at least to some extent, will always be effected in practicing the present process. It is impracticable to define the narrow zone on opposite sides of the theoretical point within 'which the-process might ,not have a degree of utility warranting its 'prac- `tice .on a commercial scale. The limits of such narrow zone would not be critical and would vary with starting mixtures of diiierent parafns and their relative proportion, and more particularly with the degree of purication desired; but as explained above the present process would always be operative to effect some worth-while degree of separation. Where the starting mixture is of the S-type and its composition is sufficiently close to the above discussed theoretical point so that treatment of the mixture does not give a commercially worth-while improvement, the degree of separation may be improved by operating at a different temperature or by first changing the composition of the starting mixture in some other manner, for example, by distillation or by adding to the mixture more of one of the con'- stituents, after which treatment may be carried out according to the present process to effect a high degree of purication.

The type oi. starting mixture to` which the present process usually will be applied in actual practice is one which contains the desired paraiiin in more or less concentrated form initially and which contains as impurity not merely one other parain but a plurality of paraiiins in minor amounts. For example, the charge may be a paraiinic fraction containing the desired paraflin .in a concentration exceeding 80%, say 90% or '95% or the like, together with several other 4Daraiiins as impurity. As a general rule, these parains will boil suiilciently close to the boiling point of the desired paraffin that purification by distillation will be exceedingly difficult cr substantially impossible as a practical matter. .With such mixtures purification Vwill always be effected 'by the present process, aside and apart from the several reasons above discussed as to why a separation will always be obtained. This is due the desired hydrocarbon in a substantially purified form.

A preferred method of conducting the process comprises carrying out the treatment by percolating the starting mixture of hydrocarbons through a column of the adsorbent. Preferably a large proportion of adsorbent is used relative to the amount of hydrocarbon material to be treated, After all of the charge has passed into the adsorbent, itmay be followed by a describing agent. such as a polar organic liquid (for example, alcohol or acetone) or water, to displace the adsorbate. vDesorption may also be accomplished, if desired, by using a non-polar liquid such as an aromatic or a saturated hydrocarbon in sufficiently large amount to displace the adsorbate. IThe use of a desorbing agent is necessary where the desired component is the one which is selectively adsorbed. In the other case where the desired component is not preferentially adsorbed and therefore appears in lhighest purity as the iirst portion of efliux or iiltrate from the column, a desorbing agent is ,not necessarily required provided suiicient charge is -used to wet all of the adsorbent and produce a filtrate. in either case Ythe eiiiux lfrom the column s'collected inv separate fractions as desired in order to segregate the portion'which 'has the desired purity.

With hydrocarbons that behave as illustrated in Figure l, the first portion of eiux or filtrate will comprise the less strongly adsorbable component in a relatively high state of purity as compared to the charge. Succeeding portions will decrease in purity and, as the adsorbate is displaced from the gel, the filtrate will become less pure than the charge. However, with this type of system the component which is preferentially adsorbed will never be obtained in high concentration but only in concentrations below that represented by point M.

With the type of system as illustrated by Figure .2, the first portion of filtrate will be relatively rich, as compared to the charge, ,in the less ad sorbable component regardless of the charge composition. Succeeding portions will become less and less rich in this component, eventually becoming enriched with respect to the more adsorbable component as it is displaced from the gel by means' of the desorbing agent. Thus it is possible to obtain one component in concentrated form as the rst portion of filtrate and also to obtain the other component in enriched form as the last portion of ltrate. The degree of separation will depend to some extent upon the amount of adsorbent used.

When the system is the type shown in Figure 3, the rst portion of iiltrate will be rich with re- A spect to the less adsorbable component and `the Example I A sample of the best grade of synthetic `normal vhexane available commercially was found to contain 5 mol percent of other paramnic material as impurity. This starting material was treated with silica gel by percolation down through a column of 1.3 inch internal diameter packed to a height of about 45 inches with 675 grams of 28-200 mesh silica gel. The column was provided with a water jacket and ice water was continuously circulated therethrough to absorb the heat generated due to wetting of the gel and to maintain the temperature substantially constant within a few degrees of ice temperature. A total of 110 ml. of the starting material was passed into the gel and this was followed by alcohol in amount sufficient to displace substantially allof the hydrocarbon from the gel. The rst portion of filtrate amounting to 4l ml. or about 37% of the charge was normal hexane in a purity averaging 98 mol percent as determined by the freezing point method.

Example II A sample of synthetically prepared 2,5-dimethylhexane of 90 mol percent purity was treated in the manner described in Example I, a total of 90 ml. being used as the charge. A first cut of 35 mi. of the ltrate, amounting to about 39%. of the charge, was obtained in a purity of 95 mol percent. A higher purity could have been obtained by taking a smaller rst cut or by retreating the rst cut with regenerated gel.

Example III 200 ml. of n-octane containing 1.5 mol percent of parainic material as impurity was treated with 730 g. of 28-200 mesh silica gel. The first cut which amounted to 7% of the charge had a purity of 99.83 mol percent. The -60% portion of the charge had an average purity of 99.4 mol percent.

y Example IV 'I-he starting material was 97.2 mol percent 2,3,4-trimethylpentane containing mainly 2,3,3- trimethylpentane as the impurity. 100 ml. of this material was treated with 675 g. of'silca gel as in'Example I and the following results were obtained:

Vol. Per- Purity, (iut Nn. cent of mol Pcr- Charge cent These results show that the present method is capable of preparing an extremely pure product.

Example V 87 ml. of starting material containing 93 mol percent of 2,3,3-trimethylpentane was treated with 675 g. of silica gel as in previous examples. The impurities in the charge were chiey dimethylhexanes. The iirst cut, amounting to 7.6% of the charge, had a purity of 99.3 mol percent.

Example VI Example VII A column having an internal diameter of about Cil 1/2 inch and a height of 3 feet was used. The column was provided with a water jacket through which ice water was circulated. 50 m1. of a mixture composed of 90% 2,3,3-trimethylpentane and 10% 2,2,4-trimethylpentane was treated with 84 g. of silica gel by percolation through the column. The behavior of these components is illustrated in Figure 2. The charge was followed by alcohol in order to force the hydrocarbon through the gel. The first portion of filtrate amounting to 20% of the charge was 98% pure 2,3,3-trimethylpentane. 72% of the charge was obtained as ltrate having a purity higher than that of the charge.

Example VIII In another run carried out as in Example IX using the same amounts of charge and gel, a mixture of 90% 2,2,4-trimethylpentane and 10% noctane yielded a first cut, amounting to 20% of the charge, which was better than 99.5% pure 2,2,4-trimethylpentane. These components are the ones upon which Figure 1 is based.

Example IX This run diiered from the previous one only in that the charge composition was reversed so that it was composed of 90% n-octane and 10% 2,2,4-trimethylpentane. The first fraction of ltrate comprising 10% of the charge was 95% pure n-octane.

Example X This run was carried out by percolating 24 ml. of a mixture composed of 90% 2,2,3-trimethylbutane and 10% 2,4-dimethylpentane through 84 g. of silica gel as in Example IX. The rst 10 m1. of filtrate, or about 42% of the charge, was the 2,2,3-ccmpound in a purity better than 99.5%.

Example XI The charge was n-heptane containing 5% 2,4- dimethylpentane. 25 ml. of the charge was passed through g. of silica gel as in Example IX. The rst cut amounting to 16% contained 2% 2,4- dimethylpentane as impurity.

Example XII This run differed fromkthe previous run only in that the charge composition was reversed, the charge being 2,4-dimethylpentane containing 5% n-heptane. Two 12% cuts of the first portion of filtrate were separated and these contained 1.7% and 3.4%. respectively, of n-heptane as impurity.

Example XIII In this run 24 ml. of n-heptane containing 5% 2,3-dimethylpentane was percolated through 80 g. of silica gel as in Example IX. Two cuts were taken, each representing about 17% of the charge. and these were found to be 98.5% and 96% pure, respectively.

In practicing the invention it generally will be desirable to reactivate the adsorbent after it has been used in order that it may be used again. This may be done by blowing the adsorbent with hot inert gas or air to drive oi the adsorbed hydrocarbons or to drive ofi the desorbing agent if one has been used.

The temperature at which the adsorption 0peration is carried out may affect the eiiiciency of the separation and it often will be the case that a poorer separation will be obtained at elevated temperature. ably conducted at room temperature or below to insure a better separation. This generally will The operation therefore is prefer- 9 necessitate the provision of some means for removing any heat generated due to wetting of the adsorbent as, for instance, by providing means for circulating a cooling medium around the adsorbent column.

This application is a continuation-in-part of my co-pending application Serial No. 643,762, iiled January 26, 1946, now abandoned.

Having described my invention, what I claim and desire to protect by Letters Patent is:

1. A process of separating two parain hydrocarbons having the same molecular weight which comprises subjecting a saturate mixture of such hydrocarbons to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively ads-orbing one of said hydrocarbons, and separating from the silica gel a fraction containing the other hydrocarbon in a more nearly pure state.

2. A process according to claim 1 wherein said paraffin hydrocarbons are each isoparaiiins.

3. A process for kpurifying a paraffin hydrocarbon which contains in admixture therewith a small amount of another parafn hydrocarbon of the same molecular weight which comprises subjecting a saturate mixture of said hydrocarbons to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively adsorbing said other hydrocarbon which is present in small amount, and separating from the silica gel a fraction containing the desired parain hydrocarbon in relatively pure state.

4. A process according to claim 3 wherein said paraffin hydrocarbons are each isoparaiins.

5. The process of separating two isomeric parainn hydrocarbons from a saturate mixture containing them, which hydrocarbons are present in such proportion as to have substantially different adsorbabilities, which comprises subjecting. such mixture to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively adsorbing one of said hydrocarbons4 and separating from the silica gel a fraction containing the other hydrocarbon in a more nearly .pure state.

6. In a process of separating a saturate liquid hydrocarbon mixture comprising two isomeric parain hydrocarbons and in which the two hydrocarbons have different adsorbabilities when they are present within a certain range of proportions, the steps which comprise subjecting such mixture in which the proportions of said paraflin hydrocarbons are within such proportion range to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively adsorbing one of said hydrocarbons, and separating from the silica gel a fraction containing the other hydrocarbon in more nearly pure form.

7. In a process of separating a saturate liquid hydrocarbon mixture comprising two .parafn hydrocarbons, A and B, of the same molecular weight and in which hydrocarb-on A has a greater adsorbability than hydrocarbon B when A is present in small amount, the steps which comprise subjecting such mixture containing a small amount of A and a large amount of B to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively adsorbing hydrocarbon A, and separating from 10 the silica gel a fraction containing hydrocarbon B in a relatively pure state.

8. In a process of separating a saturateliquid hydrocarbon mixture comprising two paraffin hydrocarbons, A and B, of the same molecular weight and in which hydrocarbons A and B have essentially the same adsorbability when they are present in a certain denite proportion, the steps which comprise subjecting such mixture of said p-arain hydrocarbons in which the proportion of A to B is substantially less than such denite proportion to treatment in liquid phase with an adsorbent consisting essentially of silica gel, thereby selectively adsorbing hydrocarbon A, and separating from the silica gel a fraction containing hydrocarbon B in a relatively pure state.

9. A process according to claim 8 in which the two paraffin hydrocarbons are each branched chain parains.

10. A process according to claim 8 in which the hydrocarbon A is a branched chain paraffin and hydrocarbon B` is a straight chain parafiin.

11.A process for purifying a paraffin hydrocarbon which contains in admixture therewith as impurity another paraiin hydrocarbon of the same molecular weight, said paraillns having the same adsorbability when admixed in a certain dei'inite proportion, which comprises introducing a saturate mixture of said paraiilns containing the desired paralin in major proportion substantially in excess of said certain denite proportion in liquid phase into a body of adsorbent consisting essentially of silica gel, thereby Selectively adsorbing the paraffin which is present as impurity, and separating from the silica gel a filtrate fraction which contains only a portion of the total hydrocarbons introduced, thereby obtaining the desired paraffin in more nearly pure state.

12. A process for purifying a paraffin hydrocarbon which contains in admixture therewith as impurity less than 20% of an isomeric parafiin hydrocarbon, said parafnns having the same adsorbability when admixed in a certain definite proportion, which comprises introducing a saturate mixture of said .parauns containing the second-named paraiiin in a proportion substantially less than said certain definite proportion in liquid phase into a body of adsorbent consisting essentially of silica gel, thereby selectively adsorbing the second-named paraffin, and separating from the silica gel a filtrate fraction which contains only a portion of the total hydrocarbons introduced, thereby obtaining the firstnamed paraffin in more nearly pure state.

ALFRED E. HIRSCHLER.

` REFERENCES orrnn The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,306,610 Barrer Dec. 29, 1942 2,425,535 Hibshman Aug. l2, 1947 2,442,191 Black May 25, 1948 OTHER REFERENCES Mair et al., Oil 8; Gas J., Sept. 19, 1935, pages 29, 30 and 32. 

1. A PROCESS OF SEPARATING TWO PARAFFIN HYDROCARBONS HAVING THE SAME MOLECULAR WEIGHT WHICH COMPRISES SUBJECTING A SATURATE MIXTURE OF SUCH HYDROCARBONS TO TREATMENT IN LIQUID PHASE WITH AN ADSORBENT CONSISTING ESSENTIALLY OF SILICA GEL, THEREBY SELECTIVELY ADSORBING ONE OF SAID HYDROCARBONS, AND SEPARATING FROM THE SILICA GEL A FRACTION CONTAINING THE OTHER HYDROCARBON IN A MORE NEARLY PURE STATE. 